A novel approach of ball milling and oxalic acid was employed to modify sludge-based biochar (BOSBC) to boost its activation performance for peroxymonosulfate (PMS) towards efficient degradation of sulfamethoxazole (SMX). 98.6% of SMX was eliminated by PMS/BOSBC system within 60 min. Furthermore, PMS/BOSBC system was capable of maintaining high removal rates for SMX (>88.8%) in a wide pH range from 3 to 9, and displayed a high tolerance to background electrolytes including inorganic ions and humic acid (HA). Quenching experiments, electron paramagnetic resonance (EPR) analysis, in-situ Raman characterization and PMS decomposition experiments confirmed that the non-radicals of O-1(2) and surface-bound radicals were the main contributors to SMX degradation by PMS/BOSBC system. The results of ecotoxicity assessment illustrated that all transformed products (TPs) generated in PMS/BOSBC system were less toxic than that of SMX. After five reuse cycles, PMS/ BOSBC system still maintained a high removal rate for SMX (77.8%). Additionally, PMS/BOSBC system exhibited excellent degradation performance for SMX in various real waters (Yangtze River water (76.5%), lake water (74.1%), tap water (86.5%), and drinking water (98.1%)). Overall, this study provided novel insights on non-metal modification for sludge-based biochar and non-radical mechanism, and offered a feasible approach for municipal sludge disposal.